Halogenated heterocyclic insect toxicant and process of preparing same



United States Patent HALOGENATED HETEROCYCLIC INSECT TOXI- CANT ANDPROCESS OF PREPARING SANIE Samuel Barney Soloway, Denver, Colo.,assignor, by mesne assignments, to Shell Development Company,Emeryville, Calif., a corporation of Delaware No Drawing. ApplicationFebruary 4, 1954,

Serial No. 408,307

3 Claims. (Cl. 260-327) This invention relates to the production of anovel chemical compound having particular utility as an insecticide, andis a continuation-in-part of copending application Serial No. 63,626,filed December 4, 1948.

More particularly, the present invention relates to the production ofthe sulfoxy derivative of the Diels-Alder adductof*hexachlorocyclopentadiene and bicyclo( 2.2.1)- 2,5-heptadiene, and inits substantially pure condition is a white solid melting at about 202C. with decomposition, of the following structural formula:

01 n 01 H l H 01001 11011 s=o Cl I H l 7 01 n The foregoing novelcompound is more directly derived, in accordance with the presentinvention, by oxidation of the episulfido derivative of the Diels-Alderadduct of hexachlorocyclopentadiene and bicyclo-(2.2.1)-2,5- heptadienedescribed and claimed in the aforesaid copending application, andunexpectedly the episulfoxy compound exhibits double the toxicity towardinsects, such as flies, than does the episulfido compound from which itis directly derived.

The parent episulfido compound may be prepared, as described in theaforesaid copending application, by reacting hexachlorocyclopentadienewith bicyclo-(2.2.l)- 2,5-heptadiene, suitably by heating, to form theirequimolar Diels-Alder adduct, reacting the latter in a solvent, such ascarbon tetrachloride, with bromine in like solution to form the6,7-dibromo derivative of said adduct, and then reacting said derivativewith sodium sulfide, such as by refluxing it with Na2S.9H2O in ethanol,to convert it to the 6,7-episulfido derivative by removing the bromineatoms and introducing a sulfur atom.

The 6,7-episulfoxy compound of the present invention may be prepared byoxidizing the aforesaid 6,7-episulfido derivative, with an organic peracid such as peracetic or perbenzoic acid, as follows:

To a solution of 102 grams of the aforesaid episulfido compound in 570ml. of benzene there was added 32 ml. of a 67% peracetic acid solutionover a 40-minute period while stirring rapidly. A temperature of 40 C.was maintained by controlling the rate of addition of the per acid.After an additional period of stirring, the reaction mixture was cooledand the separated solids were collected on a filter and washedsuccessively with water, dilute sodium bicarbonate solution, and wateragain. After drying, the product amounted to 60 grams. By concentratingthe benzene portion of the filtrate to 30 ml., collecting the separatedsolids, and recrystallizing the latter from benzene, there was obtainedan additional 30 grams of product. The product is a white solid, M. P.202 C., with decomposition, which is sparingly soluble in benzene andhexane.

Analysis.Calculated for C12HaClsOS: C, 34.85; H, Cl, 51.5. Found: C,34.79; H, 1.92; CI, 51.47,

Relative Compound: toxicity, percent Chlordane (standard) EpisulfideEpisulfoxide 320 The compound of the present invention also exhibitspotency against other insects, and may be used in all the ways customaryin the art either alone or in combination with other insecticides, andwith the aid of the usual insecticidal adjuvants or carriers, such as bydissolving the insecticide base oils normally employed, as was done toobtain the foregoing comparative test data, or in combination withfinely divided carriers to produce wettable and nonwettable insecticidedusts, or in the presence of emulsiflying agents in combination withwater or with water and 01 I claim:

1. The compound l,2,3,4,10,l0-hexachlor0-6,7-episulfoxyl,4,4a,5,6,7,7,8,8a octahydro 1,4,5,8 dimethanonaphthalene melting withdecomposition at about 202 C., and having the following structuralformula:

H Cl l I H I Cl C] HCH S=O Cl\ I H l 5 2. The process of forming thecompound of claim 1 which comprises oxidizing the 6,7-episulfidoderivative of the Diels-Alder adduct of hexachlorocyclopentadiene andbicyclo-( 2.2.1 )-2,5-heptadiene.

The method which comprises applying to insects and their habitats thecompound of claim 1.

No references cited.

1. THE COMPOUND1,2,3,4,10,10-HEXACHLORO-6,7-EPISULFOXY-1,4,4A,5,6,7,7,8,8A-OCTAHYDRO-1,4,5,8 - DIMETHANONAPHTHALENE MELTING WITH DECOMPOSITION AT ABOUT 202*C., AND HAVING THE FOLLOWING STRUCTURAL FORMULA: